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Dimethyl (±)-(1s*,2r*,3s*)-[3-Phenyl-1-(N-Phenylcarbamoyloxy)-2, 3-Epoxypropyl]-Phosphonate, T. Boehlow, A. De La Cruz, N. Rath, C. Spilling

Chemistry & Biochemistry Faculty Works

The crystal structure of the racemic title compound, C18H20NO6P, m.p. 428-431 K, has been determined by X-ray diffraction. The title compound consists of a tetrahedral P atom bonded to two methoxy groups, and an alkyl chain. The alkyl chain was substituted at position 1 with a carbamate and with an epoxide at positions 2 and 3. The relative configuration of the 1-carbamate and 2,3-epoxide substituents was confirmed as anti (1S,2R,3S). The crystal structure contains an enantiomeric pair with two intermolecular hydrogen bonds in a 14-membered ring. The hydrogen bonds are formed between the P=O of one enantiomer and the N-H …

Dimethyl (±)-(1s*,2r*,3s*)-[3-Phenyl-1-(N-Phenylcarbamoyloxy)-2, 3-Epoxypropyl]-Phosphonate, T. Boehlow, A. De La Cruz, N. P. Rath, C. D. Spilling

Christopher Spilling

Dimethyl (±)-(1s*,2r*,3s*)-[3-Phenyl-1-(N-Phenylcarbamoyloxy)-2, 3-Epoxypropyl]-Phosphonate, T. Boehlow, A. De La Cruz, Nigam P. Rath, C. D. Spilling

Nigam Rath

Probing The Intermolecular Hydrogen Bonding Of Water Molecules At The Ccl4/Water Interface In The Presence Of Charges Soluble Surfactant, D. E. Gragson, G. L. Richmond

Chemistry and Biochemistry

The molecular structure and hydrogen bonding of water molecules at the CCl₄/water interface in the presence of a charged soluble surfactant has been explored in this study using vibrational sum frequency generation. By examining OH stretching modes that are highly sensitive to the local hydrogen bonding environment it is found that water molecules at the CCl₄/water interface both in the presence and absence of a charged soluble surfactant are predominantly in a tetrahedral arrangement much like the structure ofice. Isotopic dilution studies have been employed to further characterize this icelike interfacial structure. Ablueshift ofapproximately120 cm^{-1 …}

Nucleotide Or Nucleoside Photoaffinity Compound Modified Antibodies, Methods For Their Manufacture And Use Thereof As Diagnostics And Therapeutics, Boyd E. Haley, Heinz Köhler, Krishnan Rajagopalan, Gabriela Pavlinkova

Chemistry Faculty Patents

Sites on antibodies having affinity for photoaffinity compounds, in particular purine or azidopurine containing compounds are taught. These sites provide for the site-specific attachment of nucleotide photoaffinity compounds to antibodies, e.g., ATP- or GTP-analog photoaffinity compounds by photochemical means. These nucleotide photoaffinity compounds may additionally be attached to molecules having a desired therapeutic or diagnostic activity, and the resultant conjugates used as diagnostics or therapeutics.

Proton Nuclear Magnetic Resonance Investigation Of The [2fe-2s]1--Containing “Rieske-Type” Protein From Xanthobacter Strain Py2, Richard C. Holz, Frederick J. Small, Scott A. Ensign

Chemistry Faculty Research and Publications

Proton NMR spectra of the Rieske-type ferredoxin from Xanthobacter strain Py2 were recorded in both H₂O and D₂O buffered solutions at pH 7.2. Several well-resolved hyperfine-shifted ¹H NMR signals were observed in the 90 to −20 ppm chemical shift range. Comparison of spectra recorded in H₂O and D₂O buffered solutions indicated that the signals at −11.4 (L) and −15.5 (M) ppm were solvent-exchangeable and thus were assigned to the two histidine N^ε2H protons. The remaining observed signals were assigned based upon chemical shift, T₁ values, and one-dimensional …

34. Shunsuke Murahashi, Otto Vogl, Mikiharu Kamachi, Koichi Hatada

Emeritus Faculty Author Gallery

No abstract provided.

Icris '96: Controlled Organization And Molecular Dynamics Of Polymers, Uji, Kyoto, Japan, Otto Vogl, Masaki Tsuji

Emeritus Faculty Author Gallery

No abstract provided.

Freezing Of Confined Water: A Bilayer Ice Phase In Hydrophobic Nanopores, Kenichiro Koga, Xiao Cheng Zeng, Hideki Tanaka

Xiao Cheng Zeng Publications

Molecular dynamics simulations were performed to study the phase behavior of a thin film of water confined to a slit nanopore with smooth walls. A first-order water-to-ice freezing transition has been observed. The resulting ice, which is a crystal of bilayer consisting of rows of distorted hexagons, does not resemble any ice crystals found so far. The confined water contracts upon freezing when the confinement load is low ( ∼0.5 kbar) and expands when the load is high (10 kbar). The residual entropy of the bilayer ice can be calculated exactly, which is about half of the entropy of the …

The Determination Of The Crystal Structure Of 2-Methyl-2methylacrylyl-Cyclohexanone- (1,5)-Diaxaspiro Mononeopentyl By X-Ray Christallography, Joann Stevenson

McCabe Thesis Collection

Cyclohexanone, the central component of the compound 2-methyl-2-methylacrylylcyclohexanone-( l,5)-diaxaspiro mononeopentyl (see figure on page 2), serves as a solvent for oil in piston type aircraft and in natural and vinyl resins. It is used in the production of crude rubber, waxes, fats, shellac and DDT and other pesticides. Cyclohexanone also is a part of the production of adipic acid, which is used to prepare nylon and is used to prepare cyclohexanone resins via condensation to enhance the adhesive properties of products like floor paints.

Cyclohexanones are among the most accessible hydroaromatic derivatives and serve as the initial materials for the …

34. Shunsuke Murahashi, Otto Vogl, Mikiharu Kamachi, Koichi Hatada

Otto Vogl

No abstract provided.

Icris '96: Controlled Organization And Molecular Dynamics Of Polymers, Uji, Kyoto, Japan, Otto Vogl, Masaki Tsuji

Otto Vogl

No abstract provided.

Elucidation Of The Pathway Required For The Stimulation Of G6pdh Gene Expression By Insulin And Its Mimetics, Asavari Wagle

Masters Theses

Insulin, an anabolic hormone, exquisitely controls cellular physiology and metabolism by modulating the activity of key proteins which regulate metabolic and mitogenic events. Insulin activates several cytosolic proteins via a phosphorylation cascade, but only some of these proteins are required for its specific action. We have elucidated the insulin signal transduction cascade in primary rat hepatocytes, and outlined some of the events that are required for the insulin induced stimulation of glucose-6-phosphate dehydrogenase (G6PDH) gene expression. Using well-characterized and structurally different inhibitors, we show that insulin stimulation of the gene requires the IRS-1/P13K pathway and not the RAS/RAF/MAPK pathway. Gene …

Evaluation Of The Natural Biodegradation Of Aircraft Deicing Fluid Components In Soils, Laura M. Johnson

Theses and Dissertations

This research effort was conducted to analyze the biodegradation of propylene glycol (PG) and tolyltriazole in two different soil types; a sandy soil and a high clay soil. Both an automated respirometer and a high performance liquid chromatograph (H PLO) were used in the analysis. Two separate experiments were conducted. In the first experiment, one level of tolyltriazole was added to the soils to determine whether or not there was a difference in the biodegradation rates of tolyltriazole in the two soils. The respirometer results indicated that there was a significant difference between the respiration rates of the microorganisms in …

Modeling The Uptake And Transpiration Of Tce Using Phreatophytic Trees, Douglas P. Wise

Theses and Dissertations

Phytoremediation is a recent addition to the numerous methods used today to remediate ground water contaminants. It is proving more effective and efficient compared to existing remediation techniques. The use of phreatophytes, or water seeking trees, has great potential for phytoremediation. These trees are fast growing, long lived, grow their roots down to the ground water table, transpire large amounts of water, and are proven to actively remove contaminants from the soil horizon. The purpose of this research is to develop quantitative concepts for understanding the dynamics of TCE uptake and transpiration by phreatophytic trees over a short rotation woody …

A Modeling Study For The Implementation Of In Situ Cometabolic Bioremediation Of Trichloroethylene-Contaminated Groundwater., John A. Christ

Theses and Dissertations

The limitations of conventional groundwater remediation technologies have led to the development of innovative technologies which may achieve national hazardous waste site remediation goals. Before an innovative technology can be implemented in the field, remedial project managers, regulators and other stakeholders require adequate modeling tools to help assess the applicability of the technology at a particular site. This modeling study investigates how an innovative technology, in situ cometabolic bioremediation, might be implemented to remediate a TCE-contaminated site, under different site conditions. A steady-state model is developed which couples an analytical expression to simulate the effect of flow between multiple pumping …

Studies On Resolution Of Enantiomeric Dialkylaryl Sulfonium Ions With Nmr Shift Reagents, Ea-Ji-Ru Son

Masters Theses & Specialist Projects

Praseodymium(III) NMR shift reagent, which is an upfield shift reagent, is focused on for assessment of enantiomeric excess and resolution of methyl sulfonium ions. A series of alkylmethylphenylsulfonium ions were analyzed, where alkyl is ethyl (I), butyl(H), octyl (III), and benzyl(IY). The praseodymium agent gives base-lined resolution of the ortho hydrogens resonance for I and IH. All spectra are strongly temperature-dependent. I is shifted more than ED, consistent with a steric effect. Assignments for I were made by gradually increasing the concentration of the shift reagent and by analyzing R-enriched I. Racemization of R-enriched isomer of I by pyramidal inversion …

Temperature-Dependence Studies Of Photorefractive Effect In A Low Glass-Transition-Temperature Polymer Composite, Bogdan Swedek, Ning Cheng, Yiping Cui, Jaroslaw W. Zieba, Jeffrey G. Winiarz, Paras N. Prasad

Chemistry Faculty Research & Creative Works

The temperature dependence of the photorefractive effect in a polymer composite containing poly(9-vinycarbazole), tricresyl phosphate, buckminsterfullerene, and 4-(N,N-diethylamino)-β-nitrostyrene is presented. The photoconductive, electro-optic and photorefractive properties of the material have been studied in the temperature range of 22-61°C. An apparent increase of electro-optic modulation with temperature and its eventual saturation is observed. This behavior is attributed to the temperature activated orientational mobility of the second-order nonlinear chromophores. The polarization anisotropy between the p- and s-polarized readouts is consistent with what would be expected on the basis of directly measured effective electro-optic coefficients. By correlating the electro-optic value with the diffraction …

Near-Field Measurements On Contrail Properties From Fuels With Different Sulfur Content, Andreas Petzold, Reinhold Busen, Franz Peter Schroder, Robert Baumann, Markus Kuhn, Johan Strom, Donald E. Hagen, Philip D. Whitefield, Darrel G. Baumgardner, Frank Arnold, Stephan Borrmann, Ulrich Schumann

Physics Faculty Research & Creative Works

Microphysical properties of jet exhaust aerosol and contrails were studied in the near field of the emitting aircraft for different fuel sulfur contents. Measurements were performed behind two different aircraft (ATTAS test aircraft of type VFW 614 and Airbus A310-300) using fuels with sulfur contents of 6 ppm and 2700 ppm, respectively. At closest approach (plume age < 1 s), the total number concentrations exceeded the measuring range of the condensation particle counter, i.e., N > 10⁵ cm^-3. The concentration of the dry accumulation mode aerosol, i.e., predominantly soot particles, was not affected by the fuel sulfur content. At a plume age of 10 s, an increase in total number concentration (Dp > 0.01 μm) by a …

A Study Of Polycyclic Aromatic Hydrocarbons During Combustion In An Afbc System, Laura Dicken

Masters Theses & Specialist Projects

The purpose of this study was to develop the on-line method of analysis which leads to the study of polycyclic aromatic hydrocarbons (PAHs) during combustion in an atmospheric fluidized bed combustor (AFBC) system. The study of PAHs is important because they may be produced upon the combustion of coal. The US EPA prioritizes PAHs as major pollutants due to their mutagenic and carcinogenic effects. Standards of PAHs were analyzed by injection into the gas chromatograph-mass spectrometer (GC-MS). These standards were then analyzed using the on-line method. Two coals were burned in the AFBC system and effluent samples were collected. These …

Development Of An Atmospheric Fluidized Bed Combustor (Afbc), William Orndorff

Masters Theses & Specialist Projects

The relatively recent interest in the U.S. in the development of atmospheric fluidized bed combustion (AFBC) has been preceded by two main factors. First of these is the ever present problem of acid rain and growing public support for cleaner burning fossil fuels. Second is the increasing demand on public landfills and subsequent need for burning of municipal solid waste. From these factors and their corresponding influences, Western Kentucky University has the impetus and has received the financial assistance necessary to build and develop a laboratory scale AFBC system. A brief history of the events leading to this development, as …

Fundamental Investigations Of Mechanistic Pathways Of Selected Organic Reactive Intermediates, Carl Whittle

Masters Theses & Specialist Projects

Part 1 of this thesis deals with the role that it -electron density plays in the formation of it -complexes in electrophilic aromatic substitution. Using commercial and synthetic compounds of varying it-electron density, the fact that % -complexes actually exist in these species was determined by a mass spectral investigation that was designed to monitor alkyl side-chain isomerizaitons. Also, the amount of it-complex was determined for each compound by measuring the amount of alkyl carbenium ion loss in each compound's mass spectrum. Found within the systems was an internal trend showing that the greater the amount of 7t-electron density in …

Forensic Soil Analysis: Characterization Of The Sand Fraction, John Baize

Masters Theses & Specialist Projects

The purpose of this project was to develop a comprehensive analytical method for the characterization of soil by examining particle size, elemental composition, and percent organic matter in soil, and to determine its forensic applicability. In this study, five soils of varying geological locations were examined including two samples from Kentucky; two samples from Pennsylvania; and one from Washington D C A Gilson sonic sieve shaker was used to separate fractions of soil to determine particle size, and a JEOL scanning electron microscope with a Kevex EDS detector was used to determine elemental composition. These techniques coupled with percent total …

Pan, Ppn And Mpan Measurements And The Systematic Relationship Between Mpan And Macr At A Semi-Rural Site In Tennessee, George Nouaime

Masters Theses

Simultaneous measurements of peroxymethacryloyl nitrate (MPAN) and its primary and secondary precursors, methacarolein (MACR) and isoprene, were carried out for the first time in July 1995 at a semi-rural site southeast of Nashville. In addition to these compounds, peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN), other volatile organic compounds (VOCs) and supporting measurements were also collected in collaboration with other research groups. The mean concentrations of PAN, PPN, MPAN and MACR were found to be 485 pptv, 50 pptv, 30 pptv and 0.290 ppbv respectively. MP AN levels, which closely tracked those of MACR during the day, peaked and dropped earlier …

Study On The Oxygen Electrodes Of Alkaline Fuel Cells Effect Of Dopant On The Activity Of Ag/C Catalyst, Jiawei Teng

Journal of Electrochemistry

A new kind of nonnoble catalyst for the oxygen electrodes of Alkaline Fuel Cells was investigated. The AgNiBiHg/C catalyst, which was prepared by chemical reduction, was active for the cathodic reduction of oxygen in alkaline fuel cells. It was found that the catalytic activity was improved by adding Ni, Bi, Hg to Ag/C catalyst, and the maximum activity was observed at Ag50%Ni2%Bi3%Hg3%C42%(wt%). XRD inconjunction with SEM indicated that the crystalline silver turned into amorphous in the presence of doping agents and the grain size of silver was reduced. No dramatic deactivation of the catalyst occured after 5200 hours of service.

Li/Α-Sn(Hpo4)2 Cell And Its Reaction Mechanism, Yuan Lin, Runliang Cai, Haoqing Wu

Journal of Electrochemistry

The discharge mechanism of Li/αSn(HPO4)2 cell has been investigated by means of Xray diffraction, XPS and cyclic voltammetry methodes. It has been shown that the electrochemical intercalation reation exists in the cathode material. There is a new phase after some degree of intercalation. With potential step and galvanostatic techniques, the chemical diffusion cofficients of Li+ in LixSn(HPO4)2 is estimated to be 10-12～10-13 cm2·s-1.

Calculation Of The Sacrificial Anode Resistance Utilizing Boundary Element Method, Jianhua Wu, Mingxian Sun, Guangzhou Liu, Guangzhang Chen

Journal of Electrochemistry

According to a kind of mathematic model set up for the cathodic protection potential field, the boundary element method (BEM) was used to study the working state of plate sacrificial anodes which were galvanically coupled to mild steel. In situ experiment showed that the current output and resistance of sacrificial anodes could be calculated more accurately using BEM than loiyd formula. On the basis of the calculation, the cathodic protection design would be more accurate. It was also investigated that the effect of the lengthtobreadth ratio (L/B) on current output and resistance of plate zinc anodes. The results demonstrated that …

Cyclic Voltammetric Investigation Of The Axial Coordination Effects Of Pyridine On The Redox Behaviours Of (Tpp)Co, Chuanwei Yan, Xiangqui Lin, Haichao Lin, Chunan Cao

Journal of Electrochemistry

The electrochemistry of (TPP)Co in presence of pyridine was investigated in dichloroethane solution by cyclic voltammetry. Upon the addition of pyridine to the solution, two reduction peaks of Co(Ⅲ)/Co(Ⅱ) at 0.25 and -0.40 V (SCE) were observed. It was infered that the peaks were belong to the reductions of the complex compounds with one and two axial pyridine, (TPP)Co(Ⅲ)(Py) and (TPP)Co(Ⅲ)(Py)2. Even though the mole ratio of added pyridine was less than 1 the reduction of Co(Ⅲ)/Co(Ⅱ) still mainly occured at -0.40 V, which evidently resulted from pyridine adsorption on the electrodes. Besides, it was observed that the reduction peak …

The Effect Of Bismuth On Microstructure Of The Cathodic Copper Deposition Of Copper Electrorefining, Daorong Lu, Jianxing Lin

Journal of Electrochemistry

The electrocrystal formation, crystal orientation and the chemical composition of the cathodic copper deposition in the presence of Bi3+ in the electrolyte of acidified CuSO4 are studies by scanning electron microscopy, Xray diffraction, atomic absorption and EDAM. The results indicate that the Bi could′t deposit on cathode when copper electrolysed at common current density i=200 A·mol/L-2 and t=60 ℃. Bi3+ scarcely effected on the crystal orientation (220) of copper deposition. High concentration Bi3+ in the electrolyte promoted (220) growth and inhibited the other crystal orientation growth. Bi3+ effected on electrocrystal formation and the cell dimension of copper deposition.

The Effect Of Solution Composition On The Corrosion Behavior Of Electrodeposited Zinc Powder, Qingwen Li, Qin Yang, Xi Xia

Journal of Electrochemistry

Zinc powder as a widely anode material can be electrowon from ZnCl2 or ZnO+KOH media. The properties of zinc powder are likely to be modified with electrolytic conditions such as the composition of bath solution, electrolysis manner, current density and additives etc.. In this paper, we have discussed the effect of the compositions of bath solution on the microstructure and corrosion resistance of zinc powder.